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Exposure to persistent organic pollutants begins in uterine life. The study was conducted to evaluate associations between gestational diabetes mellitus and the presence of persistent organic pollutants in placenta samples. They were derived from a birth cohort study in Ourense (NW Spain). Selective pressurized liquid extraction methodologies were used to determine targeted persistent organic pollutants in placenta samples. Cleanup of extracts was performed by solid-phase extraction using EZ-POP cartridges and detection by gas chromatography coupled to tandem mass spectrometry. Statistical calculations were performed by comparing the values obtained in the case and control groups. Statistical significance was considered as p

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUG Most of organic pollutants (OPs) have the ability to interfere with biological systems causing negative effects in living beings, including humans. In the last decades, pets have been used as bioindicators of human exposure because they share the same habitat with their homeowners. We sought to determine levels of approximately 70 OPs, including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated biphenyl ethers (PBDEs), organophosphate pesticides (OPPs), polycyclic aromatic hydrocarbons (PAHs) and pyrethroids (PYRs) in plasma samples from 39 pet dogs from Ourense (north-western Spain). The results revealed that PAHs were the dominant OPs (mean value 175 ± 319 ng/g lipid weight (lw)), followed by PYRs (132 ± 352 ng/g lw), PCBs (122 ± 96 ng/g lw), OCPs (33 ± 17 ng/g lw), PBDEs (19 ± 18 ng/g lw) and OPPs (2.1 ± 2.7 ng/g lw) in plasma samples. We have previously detected the target OPs in hair samples of pets, collected simultaneously and similar trend of some OPs has been observed. Moreover, pyrene and chrysene showed correlations between levels detected in both matrices Xunta de Galicia | Ref. GRC-ED431C 2022/35

Organic pollutants (OPs) are widely distributed around the globe, their presence has become an issue of great concern in the last years due to their potential health effects. Wildlife biomonitoring of OPs has been nowadays a common approach to assess chemical exposure in wildlife and humans. In a sample of 60 wild boars (Sus scrofa) from NW Spain, we evaluated the suitability of using liver and hair samples for the assessment of exposure and bioaccumulation of polychlorinated biphenyls (PCBs) including dioxin and non-dioxin like PCBs (DLPCBs and NDLPCBs), organochlorine and organophosphate pesticides (OCPs and OPPs, respectively), polybromodiphenyl ethers (PBDEs), pyrethroids (PYRs) and polycyclic aromatic hydrocarbons (PAHs). Selective pressurized liquid extraction (SPLE) and liquid-liquid extraction (LLE) methodologies were used to determine the target OPs in liver and hair samples. Clean-up of extracts was performed by solid-phase extraction (SPE) using EZ-POP cartridges and detection by gas chromatography coupled to tandem mass spectrometry (GC-QqQ-MS/MS). We found a distribution pattern of ΣPAHs ΣOCPs ΣPYRs ΣNDLPCBs ΣOPPs ΣDLPCBs ΣPBDEs in liver and of ΣPAHs ΣOCPs ΣNDLPCBs ΣPYRs ΣOPPs ΣDLPCBs ΣPBDEs in hair. Significant correlations (p 0.050) between the socio-demographic characteristics (gender, age and place) and OP concentrations of OCPs, PBDEs, PYRs, OPPs and PAHs were detected. Moderate correlation was found between HCB, PCB28, PCB157 and chlorpyrifos contents in both hair and liver samples. On the basis of these results, our data shows the correlation and complementary information given by both biological samples.

Objectives Antenatal exposure to organic pollutants is a leading public health problem. Meconium is a unique matrix to perform prenatal studies because it enables us to retrospectively evaluate fetal exposure accumulated during the second and third trimester. The aim of the present study was to evaluate associations between organic pollutant levels in meconium and birth weight in NW Spain. Methods In this study, we quantify the concentrations of 50 organic pollutants together with the total values of the most important chemical groups in meconium using gas chromatography coupled to tandem mass spectrometry. Results Organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers were detected with the highest levels in meconium from small for gestational age newborns. It was estimated that several congeners were statistically significant (p Conclusions The occurrence of transplacental transfer can be confirmed. Prenatal exposure to organic pollutants was associated with a decrease in birth weight and, therefore, organic pollutants could have an impact on fetal growth. Nevertheless, these results need validation in larger sample sized studies.

Organic pollutants (OPs) represent a wide range of chemicals that are potentially harmful for human and wildlife health. Many of these pollutants have been identified as endocrine disruptors that can alter hormonal balance producing adverse biological effects such as neurotoxicity, reproductive disorders, carcinogenicity and hepatotoxicity. For years, hair has been selected as a non-invasive source to assess levels of animal contamination. In the present study, a multiclass screening method for determining about 60 organic pollutants in pet hair was designed and validated for qualitative and quantitative purposes. Concentrations from different classes of organochlorine, and organophosphate pesticides (OCPs, and OPPs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (NDL-PCBs and DL-PCBs), polybrominated diphenyl ethers (PBDEs) and organophosphate esters (OPEs) were identified in the selected pet hair samples from Ourense (NW, Spain). We detected most of these pollutants in the selected hair pets. The mean concentrations found ranged from 89 to 6556ng/g for OPEs, from 8.6 to 1031ng/g for PAHs, from 8.6 to 256ng/g for PBDEs, from 29 to 184ng/g for OPPs, from 0.29 to 139 for OCPs, from 0.30 to 59ng/g for NDL-PCBs and from 1.2 to 14ng/g for DL-PCBs. To our knowledge, this is the first study to document the presence of OPs in pets from North-West Spain and it could provide baseline information for future monitoring of OPs in the area.

Because forest fires are a source of polycyclic aromatic hydrocarbons (PAHs), the influence of burnt conditions is of paramount importance and has not been thoroughly studied yet. In this study, two types of forest stands (Pinus nigra and Pinus pinaster) and two shrubland systems (Erica arborea and Ulex europaeus), differing in litter properties (composition and flammability), were considered. Changes in PAH levels were analysed in unburnt and charred litter, and they were related to different levels of soil burn severity and the organic matter composition of the charred litter, including charcoal and/or ashes. For monitoring PAH levels, an analytical method to determine them in unburnt and burnt woodland samples by pressure liquid extraction using a solid phase extraction cleanup was optimized. The highest levels of PAHs were found in the charred litter of P. pinaster (especially at soil burn severity = 200–400 °C), followed by U. europaeus, which presented similar concentration than Erica arborea and, finally, P. nigra. An association between the low molecular weight PAHs and 50% burn-off temperature differential scanning calorimetry supports the idea of fire smoke as the main source of low molecular weight PAHs in charred biomass generated at temperatures of 200–400 °C. Instead, the fraction of high molecular weight PAHs is related to hydrogen-to-carbon and oxygen-to-carbon ash-free dry weight, with charring depending on their organic matter content in the burnt material. PAH mobility will depend on the solubility of the organic matter, which is higher at higher pHs. The higher risk is the transport downstream to rivers or wet systems. Copyright © 2017 John Wiley & Sons, Ltd.

The early exposure to organic pollutants (OPs) related to dietary habit or environmental exposure is a concern of growing interest in environmental health. When OPs enter the body, they can accumulate in fatty tissue and even travel through the bloodstream being able to cross the placenta and reach the fetus through the substance exchange between the mother and the child. Epidemiologic and clinical data affirm that these chemicals increase the risk of adverse effects during childhood. This article reviews and addresses one of the most relevant analytical methods for determining OPs in placenta. We discuss and critically evaluate procedures, such as solid-liquid and selective pressurized liquid extraction (SPLE). Clean-up of extracts was performed by solid-phase extraction (SPE) using EZ-POP cartridges. Detection of OPs was carried out by gas chromatography (GC) coupled to tandem mass spectrometry (MS/MS). Recoveries ranged from 52% to 94% by SPLE with estimated quantification limits between 0.15 and 2.2ng/g for organochlorine pesticides (OCPs), between 0.083 and 0.50 for organophosphate pesticides (OPPs), between 0.025 and 0.15ng/g for polychlorinated biphenyl (PCBs), between 0.015 and 0.10ng/g for polybromodiphenyl ethers (PBDEs), between 0.33 and 0.66ng/g for pyrethroids and between 0.022 and 0.87ng/g for polycyclic aromatic hydrocarbons (PAHs). Most of the target OPs were detected in twenty real placenta samples studied, with pyrethroids, PAHs and OPPs representing most of the 90% of OPs with means of 13-18ng/g versus PCBs, OCPs, and PBDEs with means4.0ng/g. The rsults of this work indicate a prenatal exposure to OPs in Galicia.

Human exposure to environmental organic pollutants (OPs) begins in the uterine life period by trans-placental transfer. Epidemiological studies have consistently demonstrated the vulnerability of human fetuses and infants to the effects of OPs because of their rapid growth and organ development, cell differentiation, and immaturity of metabolism. The aim of the present study was to evaluate the prenatal exposure to OPs characterized by different physicochemical properties using non-invasive biological samples (meconium and placenta). A total of 88 placenta and 53 meconium samples were collected in Ourense, a city located in northwestern Spain, at the delivery and after birth from mothers and their infants from the University Hospital of Ourense, respectively. Selective pressurized liquid extraction (SPLE) methodologies were used to determine the targeted OPs in the selected biological samples. Cleanup of extracts was performed by solid-phase extraction (SPE) using EZ-POP cartridges and detection by gas chromatography (GC) coupled to tandem mass spectrometry (QqQ-MS/MS). The targeted OPs were detected with the following mean level total concentration order polycyclic aromatic hydrocarbons (PAHs) > organophosphorus pesticides (OPPs) > non-dioxin like polychlorinated biphenyls (NDLPCBs) > pyrethroids (PYRs) > polybrominated diphenyl ethers (PBDEs) > dioxin like polychlorinated biphenyls (DLPCBs) > organochlorine pesticides (OCPs) for placenta and ΣNDLPCBs > ΣPAHs > ΣOCPs > ΣPYRs > ΣOPPs > ΣDLPCBs > ΣPBDEs for meconium, respectively. Significant correlations (p < .050) between the socio-demographic characteristics of the selected population (mother's parity, age, weight increase during pregnancy, place of living and smoking habits) and log transformed concentration of some of the targeted OPs (OCPs, PBDEs, PYRs, OPPs and PAHs) were detected. The results obtained shown the complementary information given by both biological samples selected. Nevertheless, additional research will be needed to gain an understanding of the trans-placental transfer of OPs, to choose the best biological matrix to evaluate the prenatal exposure to OPs in a correct way and to know their health implications.

A large portion of organic pollutants (OPs) represent a potential hazard to humans and living beings due to their toxic properties. For several years, birds have been used as biomonitor species of environmental pollution. Polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated biphenyl ethers (PBDEs), organophosphate pesticides (OPPs), polycyclic aromatic hydrocarbons (PAHs) and pyrethroids (PYRs) were assessed in body feather samples of 71 feral pigeons (Columba livia domestica) collected from Asturias and Galicia (NW Spain). The percentage of detection for all chemical groups were above 90% in studied birds. The general pattern was dominated by PAHs (mean value ± standard deviation (SD) 32 ± 15 ng/g) followed by OCPs (3.8 ± 1.1 ng/g), PYRs (3.4 ± 3.8 ng/g), PCBs (1.6 ± 1.0 ng/g), OPPs (1.3 ± 0.70 ng/g) and PBDEs (0.80 ± 0.30 ng/g). Significant differences were observed between age, location and gender suggesting different sources of exposure and accumulation pathways.

Fish oils are one of the main sources of health promoting nutrients such as n-3 fatty acids in animal and human diet. Nevertheless, they could be an important source of persistent organic pollutants (POPs). Different strategies of decontamination processes to reduce polycyclic aromatic hydrocarbon (PAH) levels in fish oils, such as solvent extraction (ethanol) and adsorbent extraction using commercially available (activated carbon) and sustainable adsorbents (mussel shell and wood ashes), were compared. Adsorption conditions were evaluated and optimized by an experimental design and the experimental results were adjusted to response surfaces. In this way, PAH removals increased with increasing of individual PAH molecular weight and they range from 80% to 100% using activated carbon and from 10% to 100% using wood ashes. Pine wood ashes showed similar removal rates to activated carbon (87%-100%) excluding F (51%) and P (42%). No PAH removal was observed using mussel shell ashes. Ethanol extraction was also optimized and showed a good performance in the extraction of PAHs. However, it does affect their ω-3 fatty acid contents. Finally, real oil samples from different fishing areas: Spain, South America, and North Europe were selected for the decontamination experiments under experimental conditions previously optimized.

Fish oil has been identified as one of the most important contributors to the levels of polychlorinated biphenyls (PCBs) in food and feed products. In this study, PCB adsorption from fish oil onto activated carbon (AC), other sustainable adsorbents (mussel shell and wood waste ashes) and organic solvent such as ethanol were compared and optimized. Regarding to adsorbents, PCBs were extracted from fish oil by a 2.0% adsorbent material dose, during 6.0 h at 25 °C. Solvent extraction was carried out using 2 × 5.0 mL ethanol by manually stirring for 3.0 min, and then by Ultrasound-Assisted Solvent Extraction (UASE) for 5.0 min. The results showed that removal rates obtained by using adsorbent materials ranged from 0.0 to 10% for marker PCBs, from 0.0 to 37% for mono-ortho-PCBs, from 0.0 to 74% for PCB11 and from 0.0 to 95% for non-ortho-PCBs. Regarding to solvent extraction, ethanol was used by manually stirring and then by Ultrasound-Assisted Solvent Extraction (UASE). The samples were then centrifuged (2000 rpm/10 min) and the alcoholic phase was removed. With this method, removal efficiencies were much better (85-116%); nevertheless, high eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) removal rates (70-78 and 71-79%, respectively) were detected. We can conclude that adsorption with adsorbents depends on the geometry of PCB congeners, as well as both type of adsorption material and their origin, and that several sorption cycles are needed. Adsorption with ethanol could be the most effective methodology but nutritional quality was impaired, what makes necessary to look for other not so polar removal solvents.

Polycyclic aromatic hydrocarbons (PAHs) are a family of toxicants that are ubiquitous in the environment. These contaminants generate considerable interest, because some of them are highly carcinogenic in laboratory animals and have been implicated in breast, lung, and colon cancers in humans. Dietary intake of PAHs constitutes a major source of exposure in humans. Factors affecting the accumulation of PAHs in the diet, their absorption following ingestion, and strategies to assess risk from exposure to these hydrocarbons following ingestion have received very little attention. This review, therefore, focuses on concentrations of PAHs in widely consumed dietary ingredients along with gastrointestinal absorption rates in humans. Metabolism and bioavailability of PAHs in animal models and the processes, which influence the disposition of these chemicals, are discussed. Finally, based on intake, disposition, and tumorigenesis data, the exposure risk to PAHs from diet is presented. This information is expected to provide a framework for refinements in risk assessment of PAHs.

Animal nutrition constitutes an important issue for the animal production industry. Products intended for animal feed may contain undesirable substances which could endanger animal health or, because of their presence in livestock products, human health or the environment. In this sense, several incidents related with the presence of persistent organic pollutants, particularly with polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), have happen in food and feed additives. Simple, fast, quantitative, and economic methods for determining PAHs and PCBs in potentially polluting feed ingredients were developed and evaluated. The methods involved liquid-liquid extraction (LLE), clean-up, and detection by liquid chromatography with fluorescence detection (LC-FD) for PAHs and gas chromatography (GC) coupled to electron capture detection (ECD) for PCBs, using tandem mass spectrometry (MS/MS) as confirmatory technique. The overall method quantification limits range from 0.020– 4.0 μg/Kg fo...

Food safety is central to any society, having important economic, social, and environmental implications. International comparisons have shown that the European Union is the world's largest producer of food and drink products. It is not surprising therefore that the Agro-food sector has major importance/influence on the economy of Europe. The first link in the agro-food chain is animal feed, and therefore the risks associated to them, as is the case of the distribution of carcinogenic polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), are of paramount importance. Simple, fast, quantitative, and economic methods for PAHs and PCBs potentially polluting feeds were developed. The PAHs were detection by liquid chromatography with fluorescence detection (LC-FD) and the PCBs by gas chromatography (GC) coupled to electron capture detection (ECD), using tandem mass spectrometry (MS/MS) as confirmatory technique. The complete data set of 27 feed samples x 13 PAH and PCB concentrations wer...

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants in the marine environment derived from uncontrolled petroleum spills, marine transports, discharges from ships, and urban runoff. The NW coast of Spain (Galicia) has a characteristic hydrography, defined by a continuous suite of estuarine systems called “Rias Gallegas”. Some of these estuaries support important industrial and urban centres while others are preserved from human influence. The PAH contents in invertebrate organisms, such as bivalves, have been widely investigated because they are good bioindicators of pollution due to their ability to filter the water. 12 PAHs were determined in canned mussels (Mytilus galloprovincialis), clams (Venerupis pullastra), cockles (Cerastoderma edule) and knives (Ensis ensis) from the Galician “Rias Gallegas” to perform a possible risk assessment on these contaminants. Pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene and benzo[a]pyrene were detected in all the selected samples by liquid chromatography coupled with fluorescence spectroscopy. With regard to benzo[a]pyrene, which represents the most potentially carcinogenic PAHs, European Regulation 1881/2006/EC fixed at 10 μg/kg of wet weight the MRL (maximum residual level) in bivalve molluscs. None of these marine invertebrates showed values higher than the MRL and therefore, they do not suppose risk for human health. Mussels hydrocarbon body burden levels were highest than exhibited by others bivalves. Some factors may determine this feature, as lipid content or habitat. Lower PAH levels of five and six benzene rings were detected in canned mussels in pickle sauce (vegetable oil, vinegar, paprika, salt and other spices) than in mussels in natural sauce (water, salt and other spices). PAHs migration from mussels to the vegetable oil in pickle sauce was verified to be the reason.

Eleven polycyclic aromatic hydrocarbons (PAHs) have been analysed in commercial milk formulae and infant cereals. Two hydroxylated PAHs metabolites (1-OH-Pyr and 3-OH-B[a]P) and their conjugates were also analysed in milk samples. To determine the selected PAH metabolites, a simple, fast quantitative and economic method was developed. This method comprising ultrasound-assisted solvent extraction, enzymatic hydrolysis, solid-phase clean-up and detection by liquid chromatography with fluorescence detection (LC–FD) and liquid chromatography tandem mass spectrometry (LC–MS/MS) as confirmatory technique. The method was evaluated by constructing calibration curves, measurement of recovery, precision and the limits of detection. The purpose of this survey was to determine the selected analytes, to assess the exposure of babies and infants and to produce data for comparison with proposed limits that were being considered at the time of the survey. The results showed that not only no samples would have exceeded the limit for benzo[ a ]pyrene which is used as an indicator for the presence of PAHs, but also no hydroxy PAH metabolites have been detected.

The assessment of historical trends in atmospheric deposition of organic contaminants by using peat samples has been reported on several occasions because these samples represent an almost ideal medium for recording temporal changes in organic contaminant deposition rates. The determination of polycyclic aromatic hydrocarbons (PAHs) in peat samples is complicated due to the high content of organic matter in peat, which affects both extraction efficiency and analytical quality. A rapid and simple method is proposed for the determination of 10 US Environmental Protection Agency indicator PAHs in complex matrices such as peat. This article reviews and addresses the most relevant analytical methods for determining PAHs in peat. We discuss and critically evaluate three different extraction procedures, such as ultrasound-assisted solvent extraction (UASE), shaking and pressurized liquid extraction (PLE). Clean-up of extracts was performed by solid-phase extraction using silica cartridges. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted, concluding that the UASE extraction method using hexane:dichloromethane (80:20) as extractant was robust enough to determine the selected PAHs in peat samples with estimated quantification limits between 0.050 and 3.5 microg/kg depending on the PAH. UASE did not demand sophisticated equipment and long extraction times. PLE involved sophisticated equipment and showed important variations in the results. The method proposed was applied to the determination of PAHs in peat samples from Xistral Mountains (Galicia, Spain).

The agronomic utility of a solid waste, waste bentonite (WB), from wine companies was assessed. In this sense, the natural characteristics of the waste were measured, followed by the monitoring of its effects on the adsorption/desorption behaviour of three quaternary herbicides in acid soils after the addition of increasing levels of waste. This was done with the intention of studying the effect of the added organic matter on their adsorption. The high content in C (294 g kg −1 ), N (28 g kg −1 ), P (584 mg kg −1 ) and K (108 g kg −1 ) of WB turned it into an appropriate amendment to increase soil fertility, solving at the same time its disposal. WB also reduced the potential Cu phytotoxicity due to a change in Cu distribution towards less soluble fractions. The adsorption of the herbicides paraquat, diquat and difenzoquat by acid soils amended with different ratios of WB was measured. In all cases, Langmuir equation was fitted to the data. Paraquat (PQ) and diquat (DQ) were adsorbed and retained more strongly than difenzoquat (DFQ) in the acid soil studied. However, the lowest retention of DFQ in an acid soil can be increased by amendment with organic matter through a solid waste from wineries, and it is enough for duplicate retention a dosage rate of 10 t/ha. Anyway, detritivores ecology can still be affected. Detritivores are the organisms that consume organic material, and in doing so contribute to decomposition and the recycling of nutrients. The term can also be applied to certain bottom-feeders in wet environments, which play a crucial role in benthic ecosystems, forming essential food chains and participating in the nitrogen cycle.

PAHs from a polluted atmosphere are generally transferred to plants by particle-phase deposition on the waxy leaf cuticle or by uptake in the gas phase through stomata. Thus, they are also present in ingredients for animal feed. Generally, toxic substances are metabolized before or after absorption through the intestinal tract. This is the case of 3-hydroxybenzo[a]pyrene, which can be found free or in its glucuronide and/or sulphate conjugate forms. This article develops a procedure to monitor the carry-over of PAHs from feed to food of animal origin based on the analysis of animal manure. Eleven PAHs and 3-hydroxybenzo[a]pyrene were measured in four animal manures (cow, horse, rabbit and pig) by liquid chromatography with fluorescence detection. benzo[a]pyrene, benzo[b]fluoranthene and benzo[k]fluoranthene were found in all the selected samples, but their total levels were not alarming (benzo[a]pyrene equivalents (microg/kg)

On Friday, September 1, 2006, the facilities of a chemicals distributor in the Spanish town of Caldas de Reis, were almost completely destroyed as a result of a fire. Comprehensive liquid chromatography-fluorescence detection (LC-FD) analyses were performed on plant foods to determine the toxic impact of this kind of accident on population. PAHs from a polluted atmosphere are generally transferred to plants by particle-phase deposition on the waxy leaf cuticle or by uptake in the gas phase through stomata. PAH levels in all samples were not alarming (total PAHs were below 4.240 ng/g) and the PAH profiles were similar, with the exception of peppers, in all vegetal materials (5-to-4 rings ratio of 1–2), suggesting the similarity in source type (the fire). PAH concentrations in plants were related to their surface exposed to air, indicating that the contribution of soil/water PAHs to plants (aerial part) accumulation was insignificant.

Atmospheric polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are persistent organic pollutants (POPs) and exist in gas and particle phases, as well as dissolved or suspended in precipitation (fog or rain). While the hydrosphere is the main reservoir for PAHs, the atmosphere serves as the primary route for global transport of PCBs. In this study, fog and rain samples were collected during fourteen events from September 2011 to April 2012 in the Xistral Mountains, a remote range in the NW Iberian Peninsula. PAH compounds [especially of low molecular weight (LMW)] were universally found, but mainly in the fog-water samples. The total PAH concentration in fog-water ranged from non-detected to 216ng·L -1 (mean of 45ng·L -1 ), and was much higher in fall than in winter. Total PAH levels in the rain and fog events varied from non-detected to 1272 and 33ng·L -1 for, respectively, LMW and high molecular weight (HMW) PAHs. Diagnostic ratio analysis (LMW PAHs/HMW PAHs) suggested that petroleum combustion was the dominant contributor to PAHs in the area. Total PCB levels in the rain and fog events varied from non-detected to 305 and 91ng·L -1 for, respectively, PCBs with 2-3 Cl atoms and 5-10 Cl atoms. PCBs, especially those with 5-10 Cl atoms, were found linked to rain events. The occurrence of the most volatile PCBs, PCBs with 2-3 Cl atoms, is related to wind transport from far away sources, whereas the occurrence of PCBs with 5-10 Cl atoms seems to be related with the increase of its deposition during rainfall at the end of summer and fall. The movement of this fraction of PCBs is facilitated by its binding to air-suspended particles, whose concentrations usually show an increase as the result of a prolonged period of drought in summer.

Dioxins include polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and part of polychlorinated biphenyls (PCBs). Only the compounds that are chlorinated at the 2,3,7, and 8 positions have characteristic dioxin toxicity. PCDDs, PCDFs and PCBs accumulate in the food chain due to their high lipophilicity, high stability, and low vapor pressure. They are not metabolized easily; however their hydroxylated metabolites are detected in feces. They cause a wide range of endocrine disrupting effects in experimental animals, wildlife, and humans. Endocrine related effects of PCDDs, PCDFs and PCBs on thyroid hormones, neurodevelopment and reproductive development were referenced. In addition, some studies of contamination of foods, bioaccumulation, dietary exposure assessment, as well as challenges of scientific research in these compounds were reviewed.

The kinetic bioconcentration of N-heterocyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons in mussels (Mytilus galloprovincialis) after short waterborne exposure was studied. Benzo[a]pyrene (BaP), its analogue azaarene 10-azabenzo[a]pyrene (AzaBaP), and their mixture (Mix), were selected to monitor the changes in water concentrations over three days. Decay of both PAHs concentrations in water after 24 h of waterborne exposure to mussels at levels of 10 and 100 μg/L follows a first order kinetic with half-lives of 4–5 h, with residual levels of PAHs below 7%. While steady-state scenarios are well studied, there is a lack of information of what happens under non-steady-state conditions, the main purpose of our paper. A synergistic bioconcentration of the mixture was found (around 800 in the mix vs. around 400 for individual PAHs at 100 μg/L of waterborne exposure). It could be explained by the following reasons. The most polar AzaBaP does not compete with the most non-polar BaP for the same tissue compartments. Whereas BaP aggregate in hydrophobic areas, AzaBaP can also do in hydrophilic areas. Moreover, a chance for complex formation between them by charge-transfer stabilization mechanisms could make possible a higher bioaccumulation as a mixture. Instead, toxicological results suggest an additive behaviour in the mixture performance, dominated by BaP, which is the key PAH controlling phase I metabolization in mussels, since is approx. three times more toxic. These experiments provide useful indications for a rapid assessment of PAHs kinetic bioconcentration in mussels.

Fish oil has been identified as one of the most important contributors to the level of Persistent Organic Pollutants (POPs) in feed products. The determination of polycyclic aromatic hydrocarbons (PAHs) in fish oils is complicated due to the fat matrix, which affects both extraction efficiency and analytical quality. This article reviews and addresses two of the most relevant analytical methods for determining 11 mutagenic and carcinogenic PAHs, as well as two EPA indicator PAHs in fish oils. We discuss and critically evaluate two different extraction procedures, such as ultrasound-assisted solvent extraction (USAE) and ultrasound-assisted emulsification-microextraction (USAEME). Clean-up of extracts was performed by solid-phase extraction using C18 and glass columns containing silica gel and florisil for USAE or only C18 for USAEME. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted and recoveries ranged from 70% to 100% by USAE and from 70% to 108% by USAEME with estimated quantification limits between 0.020 and 2.6 μg/kg were achieved. Moreover, the applicability of the selected methods was evaluated by the analysis of real samples. To our knowledge, this is the first time that USAEME has been applied to the determination of PAHs in food matrices, such as oil fish samples. The methods proposed were applied to the determination of the target PAHs in fish samples from different countries, and it was found that the low PAH contamination of the selected fish oils could mainly occur by atmospheric sources.

Animal nutrition constitutes an important issue for the animal production industry. Products intended for animal feed may contain undesirable substances which could endanger animal health or, because of their presence in livestock products, human health or the environment. In this sense, several incidents related with the presence of persistent organic pollutants, particularly with polychlorinated biphenyls (PCBs), have happen in food and feed additives. Animal feed and feed components are challenging matrices for the determination of residues and contaminants. The variability of these matrices is enormous. It ranges from relatively simple ones like those based on wheat to all kinds of by-products from agro and food industry, such as cereal oils. Firstly, this article reviews and addresses the extraction efficiency of ultrasonic assisted solvent extraction (UASE) and focused ultrasonic solvent extraction (FUSE) for determining selected PCBs in animal feed and ingredients. Detection of these pollutants was carried out by gas chromatography (GC) coupled to electron capture detection (ECD); tandem mass spectrometry (MS/MS) was used as confirmatory technique. Recoveries ranged from 70% to 98% by UASE and from 75% to 106% by FUSE with estimated quantification limits between 0.11 and 0.3 μg/kg in feeds and ingredients and between 0.2 and 0.75 μg/kg in fats. Once the method was optimised, it was applied to 18 feed samples as well as 16 ingredients. PCBs were detected in almost all the selected samples. As expected, the samples of animal origin as shell powder and fish oil showed the highest concentrations of 56 and 29 ng/g, which are equivalent to toxicological concentrations of 123 and 18 ng WHO-TEQDL-PCBs/kg, respectively. Feeds and ingredients from vegetable origin ranged from non-detected to 7.1 μg/kg. PCB 77 and 169 were the discriminant congeners in the selected samples of feed and ingredients. Samples showed that the pattern of PCBs depends on the sources of contamination.

The primary aim of the proposed work is to propose the potential sources of pollution by polycyclic aromatic hydrocarbons (PAHs) in feeds and ingredients. To reach this propose the development of a simple, fast, quantitative and economic method for determining PAHs using liquid-liquid extraction (LLE), clean-up and detection by liquid chromatography with fluorescence detection (LC-FD) in polluting feeds and ingredients was developed. The overall method quantification limits range from 0.020 to 4.0 μg/kg and analyte recoveries are between 70% and 105% with relative standard deviations (RSD) lower than 20%. Molecular patterns of PAHs were used to study their distribution in the selected samples by cluster analysis, separating them in two groups: contaminated by atmospheric or pyrolytic sources. In order to find a relationship between the nutritional composition (protein, fibre, ash and fat content), and the hypothetical toxicity of selected feeds, a partial least squared (PLS) analysis was used, showing that fibre was a major contributor. Moreover, the complete data set of 27 feed samples and 25 feed ingredients x 13 PAH concentrations were analysed by PCA to find out what ingredients were controlling PAH pollution.

Studies on the temporal deposition of polycyclic aromatic hydrocarbons (PAHs) in peatlands are scarce, and none have been carried out in the Iberian Peninsula. To address this gap, ten PAHs were determined in a short peat core (spanning the last 1000 years) sampled in NW Iberian Peninsula, by HPLC-fluorescence. Fluoranthene, pyrene, benzo[b]fluoranthene and indeno[1,2,3-cd]pyrene predominated in the upper layers (10 cm), whereas fluoranthene and pyrene were the most abundant in the lower layers (40 cm), which showed an absence of high molecular weight PAHs (benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene). Although increased PAH contents have been detected since 1700 A.D., coinciding with the beginning of the Metallurgical and Industrial Revolution, high levels of fluoranthene and pyrene were present in peat samples dating back to the 12th century A.D. The results suggest that changes in sources, type of emission (global or local) and transport could be responsible for the different PAH content and composition of the peat core. These changes are consistent with the history of the use of natural resources in the NW of the Iberian Peninsula.

Solid waste incineration has recently attracted much attention because the combustion process involved produces highly toxic organohalogen contaminants such as dioxin-like polychlorinated biphenyls (DL-PCBs) present in fly ash. This has raised the need for simple, rapid, accurate methods for monitoring PCBs in ash samples.A method for the simultaneous quantitative determination of indicator, non-ortho and mono-ortho PCBs based on ultrasound-assisted extraction with 50:50 (v/v) n-hexane/acetone was developed, validated, and subsequently applied to real samples from a mussel shell incinerator facility in Galicia. The overall method quantification limits range from 0.35 to 1.5 ng/g in fly ash waste, from 0.30 to 1.0 ng/g in bottom ashes, and from 1.0 to 2.0 ng/g in sludge samples. Mean recoveries between 70% and 105% are achieved.DL-PCBs were identified in ash and in sludge samples collected from the wastewater treatment plant of the waste incineration facility. The enrichment factors for fly ash ranged from 3.3 to 3.7. Sewage sludge was also found to contain some polychlorinated biphenyls such as PCB 77 (29 ± 5.0 ng/g; n=4) and PCB 169 (6.9 ± 0.89 ng/g; n=4), as well as three of the seven PCB-like indicators, namely: PCB 138 (14 ± 4.4 ng/g), PCB 153 (6.1 ± 1.4 ng/g), and PCB 180 (7.7 ± 3.0 ng/g). Toxicity equivalent concentrations were 0.0054 ng/g for bottom ash, 0.0264 ng/g for fly ash, and 3.6 ng/g for sewage sludge; these values are well below the limit for DL-PCBs in wastes recently set by the European Union.All samples studied contained PCBs at levels below the maximum tolerated limit established by European legislation. Based on their PCB content, the studied sewage sludge can be used as a soil amendment with no health risk. Also, fly ash and sewage sludge can be deemed stable PCB reservoirs releasing PCBs at concentrations below the regulatory cutoff to runoff water.

Polycyclic aromatic hydrocarbons (PAHs) can be formed during the refinery processes of crude petroleum. Their removal is of great importance. The same happens with other organic solvents used for the extraction of PAHs (hexane, acetonitrile...), which can be polluted with PAHs. Kinetic and equilibrium batch sorption tests were used to investigate the effect of wood ashes wastes as compared to activated carbon on the sorption of three representative PAHs from n-hexane and acetonitrile. Mussel shell ashes were discarded for batch sorption experiments because they were the only ashes containing PAHs. The equilibrium time was reached at 16 h. Physical sorption caused by the aromatic nature of the compounds was the main mechanism that governed the PAHs removal process. Our investigation revealed that wood ashes obtained at lower temperature (300 degrees C) did not show any PAHs sorption, while ashes obtained at higher temperature (500 degrees C) have adsorbent sites readily available for the PAH molecules. An increase in the molecular weight of PAHs has a strong effect on sorption wood ashes wastes. As low the wood ashes particle size as high the sorption of PAHs, as a result of differences in adsorbent sites. The performance of wood ash wastes vs. activated carbon to remove 10 PAHs from organic solvents is competitive in price, and a good way for waste disposal.

Some polycyclic aromatic hydrocarbons (PAHs), particularly those with a high molecular weight, have been classified as probably carcinogens to humans by the International Agency for Research on Cancer (IARC). The significance of the determination of PAHs is reflected by the special attention of the European Union, which is paying to regulate the maximum allowed levels of PAHs in foodstuffs such as smoked foods. Like other thermally processed foodstuffs, toasted bread can contain these carcinogenic chemicals, not only due to a contamination at source but also during toasting. In order to check PAHs generated from toasting in sandwich bread, several treatment conditions were evaluated: direct toasting (flame-toasting, coal-grilling or gas oven-toasting) or indirect toasting (electric oven-toasting). PAHs were extracted by solid-liquid extraction (SLE) and determined by liquid chromatography with fluorescence detection (LC-FD). Based on the results, the used toasted technique would strongly affect in PAH levels in the final product. No samples obtained by electric oven and toaster were polluted; otherwise the samples toasted by charcoal and flame grilling presented very important levels. Up to 350μg/kg of total PAHs were detected in toasted samples by wood flame. Differences between different ways of toasting could be ascribed to deposition of PAHs from smoke. Finally, several commercial toasted samples of bread were tested to determine PAHs. Overall, the PAH levels were very low. Benzo[a]pyrene ranged from no detectable to 0.23μg/kg.

Retention of the cationic herbicides paraquat (PQ), diquat (DQ), and difenzoquat (DFQ) in two vineyard soils with a different management history and retention capacity was examined. The influence of copper on the ability of the soils to retain the herbicides was determined by comparing the results of adsorption and desorption tests on untreated and Cu-enriched soil samples, and also on soils that were previously treated with EDTA to extract native copper. The three herbicides were strongly adsorbed by both soils. Soil 1 exhibited linear adsorption isotherms for PQ and DFQ with partition coefficients, KD, of 1.28 x 103 and 1.37 x 103 L kg-1, respectively, and a Freundlich-type isotherm for DQ with a linearized partition coefficient, KD*, of 1.01 x 103 L kg-1. On the other hand, soil 2 exhibited curved isotherms and smaller KD* values (viz. 106, 418, and 28 L kg-1 for PQ, DQ, and DFQ, respectively). Using EDTA to extract copper from the soils released new sites for the herbicides to bind. The three herbicides exhibited strong hysteresis in the adsorption-desorption process. Extracting copper decreased the percent desorption of PQ and DQ; on the other hand, it decreased the affinity of DFQ for the resulting vacant adsorption sites. Similarly, competitive adsorption tests with copper and the herbicides revealed that the metal was only capable of displacing DFQ from adsorption sites. The behavior of this herbicide in the soils was consistent with a specific adsorption model. The disparate behavior of the two soils toward the herbicides was a result of the adsorption sites in soil 1 being less extensively occupied than those of soil 2 in the adsorption tests. The effect of copper on the adsorption of DFQ in the two soils was acceptably reproduced by an adsorption model involving Coulombic and specific sorption with competition from the metal.

Organophosphate esters are used in multitude of applications such as flame retardants, plasticizers and lubricants. In recent years concerns have been raised in regards to the environmental impact of some of the more commonly used phosphoric acid triesters, because many of them are toxic and persistent. Liquid-liquid extraction and ultrasound-assisted solvent extraction followed by liquid chromatography coupled to tandem mass spectrometry detection (LC-MS/MS) were used for the determination of nine priority organophosphate esters in waste and surface water, as well as in sediment samples for first time in Austria. Recoveries ranged from 63% to 94% in water and from 74 to 104% in sediment with estimated quantification limits between 2.6 and 7.9 ng/l in surface water, 4.1 and 13 ng/l in effluent waste water, and between 0.48 and 11 microg/kg in sediment. The validated method was applied to determine the occurrence of the selected organophosphorus flame retardants (OPFRs) and plasticizers in the aquatic environment of Austria. The impact of the discharge of waste water treatment plants into the receiving water bodies was also studied.

In recent years perfluorinated alkylated substances (PFAS) have appeared as a new class of global pollutant. Besides being an industrially important group of compounds, PFAS are regarded as highly toxic and extraordinarily persistent chemicals that pervasively contaminate human blood and wildlife throughout the world. They are therefore regarded as PBT (persistent, bioaccumulative, and toxic) chemicals. Two comprehensive methods have been developed for determination of eleven of the most environmentally relevant PFAS (seven perfluoroalkylcarboxylates, two perfluoroalkylsulfonates, and two perfluoroctanesulfonamides) in aqueous samples. The compounds were isolated by liquid-liquid extraction (LLE) and solid-phase extraction (SPE), and identification and quantification of the target analytes were achieved by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS-MS). With LLE detection limits ranged from 0.26 to 0.62 ng L(-1) for enrichment of 900-mL water samples; recovery of PFAS with a carbon chain longer than C7 was excellent (80-93%). With SPE, carboxylates with carbon chainsC10 could be extracted efficiently (70-98%) under acidic conditions, and PFOS and PFOSA could be extracted efficiently (81% and 96%, respectively) under basic conditions, resulting in MDLs between 0.25 and 0.64 ng L(-1). The LLE method was applied successfully to Austrian wastewater effluent samples.